CN115591554B - Ozone fluidized bed catalyst and preparation method and application thereof - Google Patents
Ozone fluidized bed catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 42
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 16
- 239000000440 bentonite Substances 0.000 claims abstract description 16
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 27
- 229940092782 bentonite Drugs 0.000 claims description 15
- 239000008188 pellet Substances 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 7
- 229940080314 sodium bentonite Drugs 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 229910000281 calcium bentonite Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000005507 spraying Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
An ozone fluidized bed catalyst and a preparation method and application thereof belong to the technical field of wastewater treatment and overcome the defect of poor wear resistance of the ozone fluidized bed catalyst in the prior art. The raw materials of the ozone fluidized bed catalyst comprise pseudo-boehmite, bentonite, nitric acid, acetic acid, active components and water; mixing the raw materials to prepare sol, and preparing the ozone fluidized bed catalyst by adopting a spray drying method. The ozone fluidized bed catalyst has higher wear resistance and catalytic performance.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to an ozone fluidized bed catalyst and a preparation method and application thereof.
Background
Ozone catalytic oxidation technology is used as a green and efficient advanced oxidation technology, and has been widely used in recent years. The ozone catalytic oxidation technology comprises homogeneous catalysis and heterogeneous catalysis, wherein the homogeneous ozone catalytic oxidation is a catalytic reaction using metal ions dissolved in water as a catalyst, the problem of difficult catalyst recovery exists, and the heterogeneous ozone catalytic oxidation is a catalytic reaction using solid metal, metal oxide or metal oxide supported on a carrier as a catalyst, has no problem of catalyst separation and recovery, has high application value and gradually becomes the main application flow of the technology. The choice and preparation of the catalyst is critical to the technology.
The conventional ozone catalytic oxidation process in the industry has the problems of large catalyst dosage, easy blockage and low mass transfer efficiency. The ozone catalytic oxidation fluidized bed process can overcome the problem of a fixed bed to a certain extent, but because the size of the catalyst adopted by the fixed bed process is larger, the catalyst is not suitable for being directly applied to the fluidized bed process, and therefore, a proper fluidized bed catalyst needs to be prepared.
The catalyst of the fluidized bed process generally has the problem of serious abrasion, and the long-term abrasion of the catalyst can cause the problems of rapid reduction of the catalyst performance, shorter service life of the catalyst, blockage of a reactor and the like.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect of poor wear resistance in the prior art, thereby providing an ozone fluidized bed catalyst, and a preparation method and application thereof.
For this purpose, the invention provides the following technical scheme.
In a first aspect, the invention provides an ozone fluidized bed catalyst, which comprises raw materials including pseudo-boehmite, bentonite, nitric acid, acetic acid, active components and water;
mixing the raw materials to prepare sol, and preparing the ozone fluidized bed catalyst by adopting a spray drying method.
Further, at least one of the conditions (1) to (5) is satisfied:
(1) Bentonite: (pseudo-boehmite + bentonite) = (1-10 wt%): 1, a step of;
(2) 0.1-2mol/L acetic acid is added in an amount of 1-20% of the total volume of the sol;
(3) The mass ratio of the pseudo-boehmite powder to the deionized water is (1-5) 10;
(4) The solid content of the sol is 5-50%;
(5) The active component includes at least one of a transition metal oxide and a metal salt thereof, a rare earth element, and a noble metal.
Further, at least one of the conditions (1) to (2) is satisfied:
(1) The bentonite comprises at least one of sodium bentonite, calcium bentonite and organic bentonite; preferably sodium bentonite;
(2) The active component is a single metal salt or a multi-metal salt, preferably a bimetallic salt, more preferably, the active component is copper nitrate and manganese nitrate, and the molar weight ratio of the copper nitrate to the manganese nitrate is (1-5): 1.
Further, the diameter of the ozone fluidized bed catalyst is between 10 and 500 mu m, and the pore volume is between 0.38 and 0.51cm 3 /g。
In a second aspect, the invention provides a method for preparing an ozone fluidized bed catalyst, comprising the following steps:
step 1, preparing raw materials into sol according to a certain proportion;
step 2, preparing the sol into pellets by a spray drying method;
and step 3, roasting.
Further, the step 1 includes: uniformly mixing pseudo-boehmite with bentonite, and then adding nitric acid, acetic acid, active components and water according to a proportion to prepare sol.
Further, in the sol preparation process in the step 1, the solution is continuously stirred and heated;
preferably, the temperature is controlled to be 40-80 ℃, the pH is controlled to be 1-5, and the stirring time is controlled to be 0.5-5h.
Further, in the step 2, the spray drying method includes: storing the sol in a slurry tank, and spraying the sol into a drying tower through a nozzle for drying;
preferably, the aperture of the nozzle is 1.0-1.5mm, the pressure of the nozzle is 4-10Mpa, and the temperature of the air inlet of the drying tower is 120-500 ℃.
Further, in the step 3, the roasting temperature is 400-700 ℃ and the roasting time is 3-6h.
In a third aspect, the present invention provides the use of an ozone fluidized bed catalyst or an ozone fluidized bed catalyst prepared according to the above method in wastewater treatment.
Nitric acid is determined by the amount required to adjust the pH of the solution to 1-5.
The technical scheme of the invention has the following advantages:
1. the invention provides an ozone fluidized bed catalyst, which comprises raw materials including pseudo-boehmite, bentonite, nitric acid, acetic acid, active components and water; mixing the raw materials to prepare sol, and preparing the ozone fluidized bed catalyst by adopting a spray drying method.
The invention adopts the mixture of pseudo-boehmite and bentonite as a carrier matrix, and the bentonite has excellent cation exchange capacity, strong dispersibility and strong cohesiveness, thus improving the catalytic performance and the abrasion resistance of the catalyst; a certain amount of acetic acid is introduced in the preparation process, so that the formed catalyst has a developed pore structure; active components are added in the preparation process of the sol, so that the impregnation stage for preparing the catalyst is omitted. The catalyst has the advantages of large specific surface area, developed pores, excellent catalytic performance and low abrasion.
2. The preparation method of the ozone fluidized bed catalyst provided by the invention comprises the following steps: step 1, preparing raw materials into sol according to a certain proportion; step 2, preparing the sol into pellets by a spray drying method; and step 3, roasting. The preparation and calcination are formed in one step, so that the impregnation process of the active components of the catalyst is omitted.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an ozone fluidized bed catalyst prepared in example 1.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of an ozone fluidized bed catalyst, which comprises the following steps:
step 1, taking 95g of pseudo-boehmite, adding 5g of sodium bentonite, uniformly mixing, adding 500ml of deionized water, 50ml of acetic acid with the concentration of 1mol/L, 23.45g of copper nitrate and 11.04g of manganese nitrate solution (50 wt%) and adding a proper amount of nitric acid in the mixing process to adjust the pH value to 3, and simultaneously heating the process at the temperature of 40 ℃ for 1 hour, thereby obtaining the required sol.
Step 2, storing the sol in a slurry tank of a spray drying device, and spraying the sol into a drying tower through a nozzle for drying; the aperture of the nozzle is 1mm, the pressure of the nozzle is 6Mpa, and the temperature of the air inlet of the drying tower is 300 ℃.
And step 3, collecting the prepared alumina pellets, and roasting for 5 hours at the temperature of 500 ℃ to obtain the catalyst after roasting.
The catalyst prepared in this example has a specific surface area of 220m as shown in FIG. 1 2 /g。
Example 2
The embodiment provides a preparation method of an ozone fluidized bed catalyst, which comprises the following steps:
step 1, taking 90g of pseudo-boehmite, adding 10g of sodium bentonite, uniformly mixing, adding 400ml of deionized water, 90ml of acetic acid with the concentration of 0.5mol/L, 23.45g of copper nitrate and 11.04g of manganese nitrate solution (50 wt%) and adding a proper amount of nitric acid in the mixing process, adjusting the pH value to 3.5, and simultaneously heating the process at the temperature of 80 ℃ for 1 hour, thereby obtaining the required sol.
Step 2, storing the sol in a slurry tank of a spray drying device, and spraying the sol into a drying tower through a nozzle for drying; the aperture of the nozzle is 1.0mm, the pressure of the nozzle is 8Mpa, and the temperature of the air inlet of the drying tower is 300 ℃.
And step 3, collecting the prepared alumina pellets, and roasting for 3 hours at the temperature of 500 ℃ to obtain the catalyst after roasting.
The specific surface area of the catalyst prepared in this example was 215m 2 /g。
Example 3
The embodiment provides a preparation method of an ozone fluidized bed catalyst, which comprises the following steps:
step 1, taking 90g of pseudo-boehmite, adding 10g of sodium bentonite, uniformly mixing, adding 500ml of deionized water, 30ml of acetic acid with the concentration of 1.5mol/L, 20g of ferric sulfate and 4.03g of zinc sulfate, adding a proper amount of nitric acid in the mixing process, adjusting the pH value to be 4.5, and heating the process at the temperature of 40 ℃ for 1 hour while stirring to obtain the required sol.
Step 2, storing the sol in a slurry tank of a spray drying device, and spraying the sol into a drying tower through a nozzle for drying; the aperture of the nozzle is 1mm, the pressure of the nozzle is 10Mpa, and the temperature of the air inlet of the drying tower is 300 ℃.
And step 3, collecting the prepared alumina pellets, and roasting for 6 hours at 400 ℃ to obtain the catalyst after roasting.
The specific surface area of the catalyst prepared in this example was 217m 2 /g。
Example 4
The embodiment provides a preparation method of an ozone fluidized bed catalyst, which comprises the following steps:
step 1, taking 92g of pseudo-boehmite, adding 8g of calcium bentonite, uniformly mixing, adding 500ml of deionized water, 50ml of acetic acid with the concentration of 1mol/L, 23.45g of copper nitrate and 11.04g of manganese nitrate solution (50 wt%) and adding a proper amount of nitric acid in the mixing process to adjust the pH value to 3, and simultaneously heating the process at the temperature of 40 ℃ for 1 hour, thereby obtaining the required sol.
Step 2, storing the sol in a slurry tank of a spray drying device, and spraying the sol into a drying tower through a nozzle for drying; the aperture of the nozzle is 1.5mm, the pressure of the nozzle is 5Mpa, and the temperature of the air inlet of the drying tower is 300 ℃.
And step 3, collecting the prepared alumina pellets, and roasting for 5 hours at the temperature of 500 ℃ to obtain the catalyst after roasting.
The catalyst prepared in this example had a specific surface area of 187m 2 /g。
Comparative example 1
The comparative example provides a method for preparing an ozone fluidized bed catalyst:
step 1, taking 100g of pseudo-boehmite, adding 500ml of deionized water, adding a proper amount of nitric acid, adjusting the pH value to 3, heating the process at 40 ℃ for 1 hour, and stirring to obtain the required sol.
Step 2, storing the sol in a slurry tank of a spray drying device, and spraying the sol into a drying tower through a nozzle for drying; the aperture of the nozzle is 1.5mm, the pressure of the nozzle is 5Mpa, and the temperature of the air inlet of the drying tower is 500 ℃.
And step 3, collecting the prepared alumina pellets, namely the catalyst carrier.
And 4, adding 11.725g of copper nitrate and 5.52g of manganese nitrate solution (50 wt%) into 500ml of deionized water to prepare a salt solution, immersing the catalyst carrier prepared in the step 3 in the salt solution, and roasting at 500 ℃ for 5 hours after the immersion is finished to obtain the required catalyst.
Comparative example 2
The comparative example provides a method for preparing an ozone fluidized bed catalyst:
and step 1, taking 95g of pseudo-boehmite, adding 5g of sodium bentonite, uniformly mixing, adding 500ml of deionized water, 23.45g of copper nitrate and 11.04g of manganese nitrate solution (50 wt%) and adding a proper amount of nitric acid in the mixing process, adjusting the pH value to 3, and simultaneously heating the process at the temperature of 40 ℃ for 1 hour while stirring to obtain the required sol.
Step 2, storing the sol in a slurry tank of a spray drying device, and spraying the sol into a drying tower through a nozzle for drying; the aperture of the nozzle is 1mm, the pressure of the nozzle is 6Mpa, and the temperature of the air inlet of the drying tower is 300 ℃.
And step 3, collecting the prepared alumina pellets, and roasting for 5 hours at the temperature of 500 ℃ to obtain the catalyst after roasting.
Comparative example 3
The comparative example provides a method for preparing an ozone fluidized bed catalyst:
step 1, taking 100g of pseudo-boehmite, adding 500ml of deionized water, 23.45g of copper nitrate, 11.04g of manganese nitrate solution (50 wt%) and 50ml of acetic acid with the concentration of 1mol/L, adding a proper amount of nitric acid in the mixing process, adjusting the pH value to 3, and heating the process at the temperature of 40 ℃ for 1 hour to prepare the required sol.
Step 2, storing the sol in a slurry tank of a spray drying device, and spraying the sol into a drying tower through a nozzle for drying; the aperture of the nozzle is 1mm, the pressure of the nozzle is 6Mpa, and the temperature of the air inlet of the drying tower is 300 ℃.
And step 3, collecting the prepared alumina pellets, and roasting for 5 hours at the temperature of 500 ℃ to obtain the catalyst after roasting.
Table 1 catalyst performance parameters
Wear index: the attrition index of the fluidized bed catalyst was determined according to standard ASTM D5757-95 using the air jet method. The specific method is that a certain amount of catalyst is filled in a wear index measuring device, after a certain flow of air is humidified, the catalyst is repeatedly purged through a wear pipe with three small holes at the bottom, and the worn and fallen catalyst fine powder is collected through a specific powder filtering and collecting device. Weighing the blown fine powder after lasting for 1 hour; the new powder filtering and collecting device is replaced, the blowing-out fine powder weight and the catalyst weight remained in the grinding damage tube are continuously purged for 3 hours under the original condition, and the abrasion index of the sample is calculated according to a formula.
Test examples
Under the sequencing batch operation mode, 1L of biochemical secondary effluent of petrochemical wastewater is added in each experiment, the air inflow is 600ml/min, the catalyst addition amount is 50g, the ozone addition amount is 50mg/L/h, and the performance of the examples and the comparative examples is tested under the condition of 1h of reaction time, and the experimental results are shown in Table 2.
TABLE 2 TOC removal from wastewater
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| TOC removal rate | 49.71％ | 31.52％ | 45.72％ | 46.17％ |
As can be seen from Table 2, the catalyst of the present invention has both high abrasion resistance and high catalytic performance, as can be seen from tables 1 and 2.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (14)
1. An ozone fluidized bed catalyst is characterized in that raw materials comprise pseudo-boehmite, bentonite, nitric acid, acetic acid with the concentration of 0.1-2mol/L, active components and water;
preparing raw materials into sol according to a certain proportion, preparing pellets from the sol by a spray drying method, and roasting to prepare the ozone fluidized bed catalyst;
bentonite: (pseudo-boehmite + bentonite) = (1 wt% -10 wt%): 1, a step of;
the addition amount of 0.1-2mol/L acetic acid is 1-20% of the total volume of the sol.
2. The ozone fluidized bed catalyst according to claim 1, characterized in that at least one of the conditions (1) - (3) is satisfied:
(1) The mass ratio of the pseudo-boehmite powder to the deionized water is (1-5) 10;
(2) The solid content of the sol is 5-50%;
(3) The active component includes at least one of a transition metal oxide and a metal salt thereof.
3. The ozone fluidized bed catalyst according to claim 1 or 2, characterized in that at least one of the conditions (1) - (2) is satisfied:
(1) The bentonite comprises at least one of sodium bentonite, calcium bentonite and organic bentonite;
(2) The active component is a single metal salt or a multi-metal salt.
4. The ozone fluidized bed catalyst of claim 3, wherein the active component is a bimetallic salt.
5. The ozone fluidized bed catalyst according to claim 4, wherein the active components are copper nitrate and manganese nitrate, and the molar ratio of the copper nitrate to the manganese nitrate is 1-5.
6. The ozone fluidized bed catalyst according to claim 1, characterized in that the diameter of the ozone fluidized bed catalyst is between 10 and 500 μm, and the specific surface area is 120 to 240 m 2 Per gram, pore volume of 0.38-0.51. 0.51cm 3 /g。
7. A method for preparing the ozone fluidized bed catalyst according to any one of claims 1 to 6, characterized by comprising the steps of:
step 1, preparing raw materials into sol according to a certain proportion;
step 2, preparing the sol into pellets by a spray drying method;
and step 3, roasting.
8. The method for preparing an ozone fluidized bed catalyst according to claim 7, wherein the step 1 comprises: uniformly mixing pseudo-boehmite with bentonite, and then adding nitric acid, acetic acid, active components and water according to a proportion to prepare sol.
9. The method for preparing an ozone fluidized bed catalyst according to claim 7, wherein the solution is continuously stirred and heated during the sol preparation process of step 1.
10. The method for preparing the ozone fluidized bed catalyst according to claim 9, wherein the temperature is controlled to be 40-80 ℃, the pH is controlled to be 1-5, and the stirring time is controlled to be 0.5-5h.
11. The method for preparing an ozone fluidized bed catalyst according to claim 7, wherein in the step 2, the spray drying method comprises: the sol is stored in a slurry tank and sprayed into a drying tower through a nozzle for drying.
12. The method for preparing an ozone fluidized bed catalyst according to claim 11, wherein the nozzle aperture is 1.0-1.5-mm, the nozzle pressure is 4-10Mpa, and the temperature of the air inlet of the drying tower is 120-500 ℃.
13. The method for preparing an ozone fluidized bed catalyst according to claim 7, wherein in the step 3, the roasting temperature is 400-700 ℃ and the roasting time is 3-6 hours.
14. Use of an ozone fluidized bed catalyst according to any one of claims 1 to 6 or prepared according to the method of any one of claims 7 to 13 in wastewater treatment.
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